In this invention, a process of thermal degradation of biodegradable bacterial polyesters poly(hydroxyalkanoate)s (PHAs) to lower molecular weight PHAs in controllable manner has been developed. The process involves using at least one additional component to `dilute` the PHAs in the thermal degradation process, so that the process can be controlled in the senses of better heat transfer, better stirring, easier working up after the reaction. The relationship of processing time and the molecular weights of the products at a certain temperature was obtained so that it is possible to obtain the desired molecular weight products in the real production under the guidance of the relationship.